Polymer bound fischer-tropsch catalysts

ABSTRACT

There is disclosed a resin-metal (complex) catalyst, a method for its preparation, activation and use in carrying out Fischer-Tropsch reactions. The complex is a resin which has attached to it a coordination compound(s) and a metal(s). The complex has utility as a Fischer-Tropsch catalyst. More specifically, the complex is useful for the gaseous conversion of synthesis gas (carbon monoxide and hydrogen) to hydrocarbons.

This is a divisional of application Ser. No. 631,698, filed July 17,1984.

TECHNICAL FIELD

This invention relates to polymer supported or polymer bound metalcomplexes which exhibit activity as Fischer-Tropsch catalysts.Specifically, this invention relates to gas phase Fischer-Tropschreactions wherein a resin metal complex catalyst is used in theconversion of synthesis gas to hydrocarbons.

BACKGROUND ART

There is a general belief by those skilled in the art of polymersupported catalysis that all types of polystyrene resins (macroreticularor gel) are inherently thermally unstable both in the presence orabsence of oxygen. The upper temperature limit often cited for use ofthese catalyst-resin systems is quoted at approximately 150° C. SeeSherrington "Polymer Supported Reactions in Organic Synthesis"; Chap.1p.27; Wiley: New York, 1980; See also: International Workshop onHeterophase Attached Homogeneous Catalysis, Grenoble, France, 1977 (CNRSand NSF) and Chauvin et al, "Polymer Supported Catalysts" Prog. PolymerSci., Vol. 5, p. 100, Pergamon Press, (1977). The present innovation isconcerned with functionalized macroreticular polystyrene that hasutility as a catalyst for vapor phase Fischer-Tropsch reactions attemperatures in excess of 200° C.

The use of a catalytic complex containing an anthranilic acid ligand forcatalytic hydrogenation is disclosed in U.S. Pat. No. 3,755,194 toAvilov et al, issued Aug. 28, 1973. The Avilov patent relates to ahomogeneous catalytic system for the hydrogenation of unsaturatedcompounds at room temperature and one atmosphere of hydrogen pressure.In this procedure a rhenium (I) complex of N-phenylanthranilic acid isemployed. However, this procedure like other homogeneous catalyticsystems has the disadvantage that it is difficult to separate thehydrogenation product from the catalyst itself with the result that thecatalyst is a contaminant or an impurity in the final product.

Substituted phosphines have been used to chemically link a catalystmetal to a polymer support. Examples of this are found in Grubbs et al,"Polymer Preprints," American Chemical Society, Division PolymerChemistry, 1972, Vol. 13, No. 2, pages 828-832 [Chem. Abs. Vol. 81,6555d (1974)] and also Grubbs et al, "J. Macromol. Sci Chem.," 1973,Vol. 7, No. 5, Pages 1047-1063, [Chem. Abs. Vol. 78, 164622r (1973)].

U.S. Pat. No. 4,230,633 discloses polymer supported metal complexeswherein the ligand is a cycloalkadienyl radical with metals from GroupVIII of the Periodic Table. This patent is concerned with the conversionof carbon monoxide and hydrogen to hydrocarbons in a liquid reactionmedium.

U.S. Pat. No. 4,292,415 discloses a crosslinked polystyrene withcycloalkadienyl ligands and Group VIII metal carbonyls having utility asa Fischer-Tropsch catalyst in liquid phase reactions. This patent doesnot suggest the critical relationships that the present invention isconcerned with, nor the specific ligands and vapor phase reactions.

Fischer-Tropsch catalysis by polystyrene supportedcyclopentadienyldicarbonyl cobalt (CpCo(CO)₂) has been reported byBenner et al, (American Chemical Society Symposium Series 152 (1981) p.165. The reaction was conducted in a medium pressure glass and stainlesssteel reactor. Benner et al suspended ##STR1## in purified n-octane toswell the resin and allow access to catalyst sites in the interior ofthe beads; no detectable reaction took place if the solvent wasexcluded. This is in contrast to the present invention in which thereaction takes place in the vapor phase without the requirement that thepolymer be swollen.

U.S. Pat. No. 4,323,698 discloses a weak base anion exchange resin whichhas been contacted with a solution of a coordination compound having atleast two ligands connected to at least one central metal atom, tochemically bond the resin to the metal atom by replacement of at leastone of the ligands of the coordination compound by a functional group ofthe weak base anion exchange resin. The complex can be used as acatalyst for hydrogenation, carbon monoxide insertion, polymerization,isomerization, vinyl ester exchange and ethylene oxidation reactionsamong others.

U.S. Pat. No. 4,144,191 discloses amine resins loaded with bimetallicclusters as novel hydroformylation catalysts. This patent is directed tothe conversion of liquid olefins to alcohols in a one-stephydroformylation process which consists of contacting an olefin, such as1-hexene in the liquid phase, with a gaseous mixture of carbon monoxideand hydrogen and the presence of a catalyst prepared by loading abimetallic cluster onto an amine resin.

U.S. Pat. No. 4,238,358 discloses the use of anthranilic acid as aligand for rhodium, palladium, platinum and ruthenium complexes. Thesecatalysts are disclosed as reduction catalysts for liquid phasereactions, i.e. the hydrogenation of olefinic and aromatic hydrocarbons.

The prior art does not disclose or suggest the use of resin metalcomplex catalysts in vapor phase Fischer-Tropsch reactions. One skilledin this art would readily realize or assume that resins, particularlypolystyrene resins would not hold up at the temperatures at which vaporphase Fischer-Tropsch reactions are conducted. See Catalysis, J. R.Anderson and M. Boudant, Eds. Chapter 4; Springer Verlag (1981).Specifically, the catalyst of the present invention operates in atemperature range from 175° to 275° C.

Synthesis gas is a mixture of carbon monoxide and hydrogen and can beproduced by the gasification of coal with steam and oxygen. Adescription of conventional methods of coal gasification is provided inMcGraw-Hill Encyclopedia of Science & Technology, 1977 Edition, Vol. 3,pages 248-249 (McGraw-Hill Book Company, New York).

Production of methane and higher hydrocarbons from coal by theFischer-Tropsch reaction typically employs a group VIII catalyst (e.g.Fe, Co and Ni) at temperatures in the range of about 200°-350° C. andpressures in the range of about 2100-3500 kPa (300-500 psi).

While these processes are successful in making synthetic natural gas oroxygenated hydrocarbons, the operating conditions leave considerableroom for improvement. The relatively severe operating conditions requirehigh capital investment and power or energy consumption. In addition,the severe conditions present many operating problems. Accordingly, acatalyst which overcomes these disadvantages of the prior art processesis to be highly commended.

The present invention provides complexes useful as catalysts whichenable Fischer-Tropsch synthesis to be achieved at mild operatingtemperatures and pressures.

DISCLOSURE OF THE INVENTION

There are three broad aspects to the present invention:

(1) novel polymer-metal complexes;

(2) a process for making the complexes, their activation, and

(3) the complexes as catalyst for Fischer-Tropsch reactions atrelatively mild conditions.

Thus, there is disclosed novel polymer-supported metal complexes of theformula: ##STR2## wherein ○P represents a crosslinked macroreticularpolystyrene resin which has a crosslink density of at least 5%;

x is 0 or 1;

L represents a ligand selected from the group consisting of bipyridyl,2-aminopyridine, 2-amino phenol, 2-imino pyridine, sodium anthranilate,and potassium anthranilate;

y is an integer from 1 through 8;

when y equals 1, M represents a Group VIII metal from the Periodic Tableand when y is from 2 through 8, M represents one or more metals selectedfrom the group consisting of Group VIII metals from the Periodic Table,manganese, potassium and sodium with the proviso that at least one M isa Group VIII metal;

R represents a hydrogen carbonyl or a halogen radical; and

n represents an integer from 3 through 24.

Further, there is disclosed a heterogeneous catalyst for Fischer-Tropschreactions conducted in the vapor phase at a temperature from 175° C. to300° C., said catalyst comprising;

a ligand selected from the group consisting of, 2-amino phenol, 2-aminopyridine, bipyridyl and sodium or potassium anthranilate, which iscomplexed with a metal compound selected from the group consisting of H₂FeRu₃ (CO)₁₃, H₂ FeOs₃ (CO)₁₃, MnCo(CO)₉, RuCl₃, Co₄ (CO)₁₂, H₄ Ru₄(CO)₁₂, K₂ Ru₆ (CO)₁₆, Ru₃ (CO)₁₂, and Fe₃ (CO)₁₂ ;

said ligand being chemically linked to a polymeric support, saidpolymeric support comprising from 0 to 20 weight percentchloromethylstyrene, 40 to 70 weight percent styrene and 20 to 40 weightpercent divinylbenzene.

Some of the complexes of this invention are compositions based upondivinylbenzene crosslinked polystyrenes in which the divinylbenzenecrosslinking is greater than 4 percent but less than 50 percent. Thismeans that the divinylbenzene crosslinked polystyrenes are prepared withfrom 4-50% divinylbenzene based on monomer charge with the remainderbeing styrene and other monomers (i.e. chloromethylated vinyl benzene).Also, polystyrene may be halogenated and then further reacted. Thus, thepolystyrene resins useful in this invention have pendant halomethylfunctionally. The polymer may be a terpolymer in that other comonomersmay be present in minor amounts.

The crosslinked chloromethylated polystyrene polymer is preferablymacroporous or macroreticular in character (i.e. pore size of about 100to 900 Å). Those skilled in the art are familiar with the manner ofobtaining a macroporous polymer rather than a microporous polymer. SeeSherrington supra.

EXPERIMENTAL

To these macroreticular divinylbenzene crosslinked chloromethylatedpolystyrene polymers are attached ligands. Conventionally, a ligand is amolecule, ion, or atom that is attached to the central atom of acoordination compound, a chelate, or other complex. For example, theammonia molecules in [Co(NH₃)₆ ]⁺⁺⁺, and the chlorine atoms in [PtCl₆]⁻⁻ are ligands. Ligands are also called complexing agents, as forexample EDTA, ammonia, etc. In the present invention the ligands aremolecules that are attached to the polystyrene polymer and are capableof complexing with metal carbonyls or halides. Ligands such asanthranilic acid or other amines, i.e. 2-aminophenol, are anchored tothe halomethylated polymer by known procedures such as stirring thepolymer with excess anthranilic acid or other amines such as dipyridylin a reaction medium such as ethyl ether, toluene, acetone, ordimethylformamide. As used herein, the term "dipyridyl" refers to the2,2' isomer, which is also known as "bipyridyl".

The polymer is recovered and then washed with appropriate solvents suchas ethanol. The polymer is then slurried in a reaction medium and thereis added thereto the metal or metal cluster carbonyl or halide compound.Representative of the single metal carbonyls useful in the presentinvention are Ru₃ (CO)₁₂, Fe₃ (CO)₁₂, and H₄ Ru₄ (CO)₁₂. Mixed metalcarbonyls such as H₂ FeRu₃ (CO)₁₃, K₂ Ru₆ (CO)₁₆, H₂ FeOs₃ (CO)₁₂, andMnCo(CO)₉ are also contemplated by the present invention. After stirringof this slurry for a suitable length of time, the polymer is recovered,e.g. by filtration, and washed and finally extracted to remove unreactedchemicals.

PREPARATION OF CATALYST FROM BOUND LIGAND AND METAL CARBONYLS

Anthranilic acid and 2-aminophenol were previously bound to polystyreneas described above. Both the polymer bound ligand (5 gm) and 0.73 gm ofRu₃ (CO)₁₂ were weighed into a 250 ml 3 neck flask; then 100 ml oftoluene was added. The flask was equipped with mechanical stirrer,thermometer, condenser, and nitrogen inlet/exit. The flask was flushedwith nitrogen and heated to the 60° C. reaction temperature. During theovernight reaction, a nitrogen filled balloon maintained the reactionflask atmosphere. When the reaction was complete, the mixture was cooledand filtered through a polypropylene cloth to isolate the resin. Theresin was washed with 500-1000 ml toluene and 200 ml hexane to removemost unreacted metal carbonyl. A 24 hour soxhlet extraction with hexaneor 1:1 THF/CH₃ OH removed residual extractables. The extracted resin wasvacuum dried at 50° C. for 3-4 hours. Synthesis of the metal complex wasconfirmed by elemental analysis, IR, weight gain, and color change.

Finally, the metal complex may be subjected to a treatment with areducing agent, e.g. sodium borohydride, while suspended in a reactionmedium. The reducing agent is used to selectively reduce the highervalence state of the metal to the lower catalytic state withoutaffecting or reducing the anthranilic acid or amine ligand present inthe catalytic complex.

Such reducing agents include, for example, sodium borohydride, metallicsodium (in ethanol), sodium hydride, and lithium aluminum hydride.

Polymeric supports in the form of beads, blocks, fibers, spheres,filaments, etc. may be used in the present invention. The use ofpolymers in the form of beads has been found to be advantageous sincethe ligand can be incorporated into such beads quite easily merely bystirring a mixture thereof in a suitable organic solvent or, if desired,with heating to a temperature as high as the reflux temperature of thesystem. The latter expedient may be employed for a better and fasterincorporation of the ligand onto the beads. Polymeric beads having asize of about 1 to 10 mm can be suitably employed, although beads havinga size as large as 2-5 cm. can also be used with advantage.

Particularly suitable, commercially available polymeric supports for usein the invention are polystyrene polymers (for example, Rohm and HaasXAD-4 Amberlite, or Dow Chemical XFS4022 resin), because of the ease ofattaching different chemical groups. Also, chloromethylated polystyrenebeads can be advantageously used as a polymeric support.

Other polymers having a reactive group can be provided with pendantfunctionality wherein, for example, anthranilic acid can be anchored tothe polymer by a condensation reaction. Examples of such polymersinclude chlorinated polystyrene in which chlorine atoms can serve asreactive groups and copolymers of styrene with other copolymerizablemonomers. In addition, they may be prepared as described in U.S. Pat.No. 2,597,437.

Further, in functional terms, the polymer support may additionallycontain reactive functionalities such as sulfonate, methanesulfonate,tosylate, carboxylate, cyanomethyl and the like, which can be readilyreacted so as to effect a condensation between the amino group of theligand and the reactive groups of the polymeric chain. Thus, within thiscontext, it is apparent that a wide variety of polymer supports can beused successfully in connection with the preparation of theheterogeneous catalytic systems of the invention.

Macroreticular resins can be synthesized by the polymerization ofstyrene, divinylbenzene and chloromethylstyrene using known procedures.The polymer crosslinks during the polymerization. Useful polymerscontain 0-15 weight percent chloromethylstyrene, 40-70 weight percentstyrene and 20-40 weight percent divinylbenzene.

Isoporous resins can be synthesized by polymerization of styrene andchloromethylstyrene. The polymer is crosslinked after polymerizationwith a SnCl₄ reaction. Chloromethylstyrene content can vary between 10percent and 90 percent in the uncrosslinked polymer. For moreinformation see, Regas and Papadoyannis, Polymer Bulletin 3, 279-284(1980) and Peppas, Bussing and Slight, Polymer Bulletin 4, 193-198(1981).

Macroporous and isoporous resins have different pore structures,swelling properties and physical properties because of the differentcrosslinking procedures. For this reason different catalytic propertiesmight be expected.

The feedstock advantageously used by the catalysts of this invention isknown as syngas or synthesis gas. Synthesis gas can be any of severalgaseous mixtures used for synthesizing a wide range of compounds. Suchmixtures result from reacting carbon-rich substances (ie. coal) withsteam (steam reforming) or steam and oxygen (partial oxidation); theycontain chiefly carbon monoxide and hydrogen, plus low percentages ofcarbon dioxide or nitrogen (less than 2.0%). The organic sourcematerials may be natural gas, methane, naphtha, heavy petroleum oils, orcoke (coal). The reactions are nickel-catalyzed steam-cracking(reforming) of methane or natural gas (CH₄ +H₂ O→CO+3H₂); partialoxidation of methane, naphtha, or heavy oils; and especially in view ofthe petroleum shortage the water-gas reaction with coke (C+H₂ O→CO+H₂).

Synthesis gas with ratios of H₂ to CO of from 1:1 to 2:1 have been founduseful in the present invention. Other ratios would be appropriate,however, those skilled in this art will realize that changes in theratio will affect the reaction in numerous ways.

REACTION SYSTEM USED FOR TESTS

Catalysts were utilized in a fixed bed reactor system. The reactor is a1.4 cm ID×38.1 cm (0.56×15 inch) 316 stainless steel tube. Duringcatalyst tests the reactor contained about 10 cc of catalyst. Reactorswere equipped with axial thermowells and a heating system capable ofmaintaining temperatures within 5° C. along the catalyst bed at 250° C.Each reactor was piped so that any of three gases could be passedthrough the bed.

1. Hydrogen (for catalyst reduction).

2. Helium (for purging).

3. Syngas (H₂ /CO=2/1).

The Fischer-Tropsch tests were conducted under the following conditionsunless specified otherwise:

Synthesis gas molar ratio--2/1 H₂ /CO

Pressure--1034 kPa (150 psig)

Temperature--250° C.

Gas hourly space velocity--200 hr⁻¹

CATALYST ACTIVATION

Activation procedures for polymer bound catalysts are the sodiumborohydride process or vacuum with hydrogen reduction.

The sodium borohydride activation procedure consists of addingunactivated catalyst to absolute ethanol in a reaction flask. Afteradding a stirring bar, sodium borohydride was added in small batches. A30 minute room temperature reaction was enough to complete thereduction. After isolation by filtration, the resin was washed withalcohol, petroleum ether and pentane. The pentane washed resin wascharged to the reactor and dried with a helium stream.

Vacuum and hydrogen reduction activation consists of heating catalyststo a temperature between 225°-275° C. in a helium flow. The catalyst wasthen placed under vacuum for 1 hour. Thereafter, a 2 hour hydrogen flowreduced the evacuated catalyst. After activation the temperature wasbrought to 250° C. and the Fischer-Tropsch reaction was initiated byadding syngas.

The catalysts may be used without activation, wherein the catalyst isplaced in the reactor, the temperature is raised to the reactiontemperature and then syngas is introduced into the reactor. It has beenunexpectedly discovered that non-activated catalyst will slowly activatein syngas with time until a steady state is achieved.

TEST DATA

Polymer bound amine ligated metal chloride and metal carbonyl complexeswere tested for Fischer-Tropsch activity. Table I sets out the resultsof the screening test which utilized different metal complexes,different supporting resins or polymers and different ligands. Thereaction conditions and reaction vessel were as previously described.All catalysts listed were not activated prior to testing unlessotherwise noted. These catalysts were initially screened to determinewhether or not they would exhibit any Fischer-Tropsch activity. Morecomplete data on activity is presented infra.

                                      TABLE I    __________________________________________________________________________    Polymer Bound Fischer-Tropsch Screening          Metal Cluster          Intended Metal                                          Fischer-Tropsch    Catalyst #          or Complex                  Ligand   Resin ++                                 Loading % by wt.                                          Activity    __________________________________________________________________________    1     H.sub.2 FeRu.sub.3 (CO).sub.13                  Anthranilic                           A     5        Yes                  Acid    2     K.sub.2 Ru.sub.6 (CO).sub.16                  Anthranilic                           A     5        Yes                  Acid    3     Ru.sub.3 (CO).sub.12                  Anthranilic                           A     5        Yes                  Acid    4     RuCl.sub.3 *                  Potassium                           A     5        Yes                  Anthranilate    5     Ru.sub.3 (CO).sub.12                  2-amino phenol                           A     5        Yes    6     H.sub.2 FeOs.sub.3 (CO).sub.13                  2-amino pyridine                           A     5.5      Yes    7     Ru.sub.3 (CO).sub.12                  2-amino pyridine                           A     5        Yes    8     RuCl.sub.3 *                  2-amino pyridine                           A     5        Yes    9     Ru.sub.3 (CO).sub.12                  2-imino pyridine                           B     5        Yes    10    HFeCo.sub.3 (CO).sub.12                  Benzyl Iodide                           C     3        No    11    Fe.sub.3 (CO).sub.12                  Dipyridyl                           B     3        Yes    12    H.sub.2 FeRu.sub.3 (CO).sub.13                  Dipyridyl                           B     6        Yes    13    H.sub.4 Ru.sub.4 (CO).sub.12                  Dipyridyl                           B     5        Yes    14    MnCo(CO).sub.9                  Dipyridyl                           B     6        Yes    15    RhCl.sub.3 *                  Dipyridyl                           B     5        Yes    16    Ru.sub.3 (CO).sub.12                  Dipyridyl                           B     5.2.sup.a                                          Yes    17    RuCl.sub.3 *                  Dipyridyl                           B     5        Yes    18    IrCl.sub.3                  Double Porphyrin                           A     N.A.     No    19    RuCl.sub.3                  Double Porphyrin                           A     10       No    20    Co.sub.4 (CO).sub.12                  Triphenyl                           B     3        No                  Phosphine    21    Fe.sub.3 (CO).sub.12                  Triphenyl                           B     3        No                  Phosphine    22    Ru.sub.3 (CO).sub.12                  Triphenyl                           B     5        No                  Phosphine    __________________________________________________________________________     .sup.a actually analyzed     *sodium borohydride activated prior to testing     ++ Resin A is a 70/30 styrene/divinylbenzene macroreticular resin     Resin B is a Dow Chemical XFS4022 20% Divinylbenzene 80% styrene     macroreticular resin     Resin C is vinyl benzyl chloride resin obtained from Ionac Inc.

All the active catalysts in Table I produced broad hydrocarbon productdistributions in conjunction with very minor amounts of oxygenates suchas methanol, ethanol and others. From Table I it is evident that benzyliodide, double porphyrins and triphenyl phosphines are unacceptableligands.

Catalyst Nos. 3, 7 and 9 after screening were subjected to an activationprocedure which consisted of one hour under vacuum at 250° C. and thenone hour under hydrogen at 250° C.

Tables II, III and IV set out CO conversion and light productselectivities for Catalyst Nos. 3, 7 and 9 respectively.

                                      TABLE II    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru.sub.3 (CO).sub.12.Anthranilic Acid - Catalyst #3    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.0   200 250 22.94                            22.94  22.56                                      2.71                                         0.00                                            74.73    2     2.0   200 250 60.02                            59.64  24.20                                      4.56                                         0.04                                            71.20    3     2.5   200 250 65.87                            65.43  23.41                                      3.60                                         0.00                                            72.99    4     3.0   200 250 71.19                            70.63  22.38                                      3.51                                         0.00                                            74.11    5     4.0   200 250 77.66                            76.99  21.44                                      3.18                                         0.00                                            75.38    6     4.5   400 250 74.85                            74.33  21.70                                      2.99                                         0.00                                            75.31    7     5.0   400 250 69.10                            68.69  22.09                                      2.95                                         0.00                                            74.96    OVERNIGHT SHUTDOWN:    CATALYST STORED UNDER HELIUM AT ROOM TEMPERATURE    8     1.0   200 250 26.25                            26.25  35.09                                      3.80                                         0.00                                            61.11    9     1.5   200 250 39.38                            39.27  34.19                                      5.73                                         0.00                                            60.08    10    5.0   200 225 52.07                            51.99  20.71                                      2.31                                         0.00                                            76.98    11    5.5   200 225 51.24                            51.15  19.12                                      2.46                                         0.00                                            78.42    __________________________________________________________________________

                                      TABLE III    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru.sub.3 (CO).sub.12.2-amino pyridine - Catalyst #7    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.5   200 250 54.27                            53.56  30.19                                      3.98                                         0.00                                            65.83    2     3.0   200 250 63.37                            62.31  29.51                                      3.61                                         0.00                                            66.88    3     3.5   200 250 62.60                            61.64  29.96                                      3.52                                         0.00                                            66.52    4     4.0   400 250 42.27                            41.79  34.07                                      3.80                                         0.00                                            62.13    OVERNIGHT SHUTDOWN:    CATALYST STORED UNDER HELIUM AT ROOM TEMPERATURE    5     1.0   200 250 44.55                            44.21  48.61                                      4.65                                         0.00                                            46.74    6     1.75  200 250 45.49                            45.16  46.42                                      4.71                                         0.00                                            48.87    7     3.0   200 225 27.19                            27.05  34.14                                      3.22                                         0.00                                            62.64    8     3.33  200 225 23.38                            23.32  30.52                                      2.77                                         0.00                                            66.71    9     5.66  200 250 40.87                            40.58  43.50                                      4.11                                         0.00                                            52.39    __________________________________________________________________________

                                      TABLE IV    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru.sub.3 (CO).sub.12.2-imino pyridine - Catalyst #9    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.25  200 250 5.88                            5.88   30.07                                      0.00                                         0.00                                            69.93    2     2.33  200 250 5.32                            5.32   27.73                                      0.00                                         0.00                                            72.27    3     4.50  200 250 5.40                            5.40   24.68                                      0.00                                         0.00                                            75.32    4     6.00  200 275 9.14                            9.15   52.28                                      0.00                                         0.00                                            47.72    __________________________________________________________________________

The data contained in Tables II, III, and IV demonstrates that catalystsaccording to the present invention have acceptable Fischer-Tropschactivity. To further demonstrate the activity of the catalysts of theinstant invention 11 active catalysts from Table I were activated andthen subjected to extensive testing for Fischer-Tropsch activity. Thisdata is set out in the following Tables V through XVI.

                                      TABLE V    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    H.sub.2 FeRu.sub.3 (CO).sub.13.Anthranilic Acid - Catalyst #1    Activated by three hours under vacuum at 250° C. and one hour    under H.sub.2 at 250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.00  200 250 31.54                            31.44  22.15                                      4.05                                         0.00                                            73.80    2     17.50 200 250 48.97                            58.55  22.12                                      2.84                                         0.00                                            75.04    3     25.00 200 250 53.72                            53.20  23.53                                      3.10                                         0.00                                            73.37    4     41.00 200 250 50.47                            49.76  25.88                                      3.39                                         0.00                                            70.73    5     47.00 200 250 49.82                            49.06  25.67                                      3.39                                         0.00                                            70.94    6     114.75                200 250 44.33                            43.25  26.91                                      3.85                                         0.00                                            69.24    7     120.50                200 250 44.49                            43.40  26.55                                      3.69                                         0.00                                            69.76    __________________________________________________________________________

                                      TABLE VI    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    K.sub.2 Ru.sub.6 (CO).sub.16.Anthranilic Acid at - Catalyst #2    Activated one hour under vacuum at 250° C. and one hour under    H.sub.2 at 250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     2.00  200 250 42.83                            41.98  19.22                                      2.87                                         0.00                                            77.91    2     4.50  200 250 45.54                            44.71  21.01                                      2.77                                         0.00                                            76.22    3     23.00 200 250 34.63                            22.74  22.74                                      3.26                                         0.00                                            74.00    4     24.00 200 250 37.20                            37.20  20.84                                      2.56                                         0.00                                            76.60    5     27.00 200 250 35.53                            35.53  22.60                                      2.65                                         0.00                                            74.75    6     47.25 200 250 33.33                            33.33  22.94                                      2.63                                         0.00                                            74.43    7     53.00 200 .sup. 275.sup.a                        51.06                            50.73  37.55                                      4.77                                         0.00                                            57.68    8     70.50 200 .sup. 275.sup.a                        59.97                            59.45  42.01                                      5.54                                         0.00                                            52.45    9     75.00 200 .sup. 275.sup.a                        59.68                            59.18  42.05                                      5.53                                         0.00                                            52.42    __________________________________________________________________________     .sup.a Pressure Rose to 180 psig

                                      TABLE VII    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    RuCl.sub.3.Potassium Anthranilate - Catalyst #4    Activated one hour under vacuum at 250° C. and one hour under    H.sub.2 at 250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     2.80  150 250 71.15                            69.66  17.59                                      2.81                                         0.00                                            79.60    2     4.08  150 250 76.90                            75.26  16.51                                      2.59                                         0.00                                            80.90    3     23.25 400 250 42.08                            42.01  17.84                                      2.04                                         0.00                                            80.12    4     27.50 400 250 40.87                            40.78  17.94                                      2.17                                         0.00                                            79.89    5     45.50 400 250 40.08                            39.98  17.37                                      2.17                                         0.00                                            80.46    6     116.75                400 250 40.12                            39.98  14.69                                      2.00                                         0.00                                            83.30    __________________________________________________________________________

                                      TABLE VIII    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru.sub.3 (CO).sub.12.2-amino phenol - Catalyst #5    Activated one hour under vacuum at 250° C. and one hour under    H.sub.2 at 250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     0.75  200 250 16.37                            16.37  43.37                                      5.35                                         0.00                                            51.28    2     2.00  200 250 47.99                            47.99  40.41                                      4.91                                         0.00                                            54.68    3     3.00  200 250 39.05                            39.05  41.05                                      4.66                                         0.00                                            54.29    4     4.00  200 250 33.94                            33.94  41.73                                      4.32                                         0.00                                            53.95    5     5.00  200 250 37.57                            37.47  43.00                                      4.32                                         0.00                                            52.68    6     20.72 200 250 37.97                            37.97  47.32                                      3.88                                         0.00                                            48.80    7     24.72 200 250 38.10                            38.10  47.15                                      4.07                                         0.00                                            48.79    8     27.00 200 275 56.21                            55.92  71.23                                      6.09                                         0.00                                            22.68    9     29.00 400 275 49.07                            48.96  75.47                                      5.76                                         0.00                                            18.76    10    45.50 400 275 44.45                            44.38  74.75                                      5.42                                         0.00                                            19.83    11    46.50 400 275 44.78                            44.70  73.95                                      5.33                                         0.00                                            20.72    12    50.00 400 250 28.67                            28.67  45.17                                      3.89                                         0.00                                            50.94    13    51.00 400 250 26.40                            26.40  49.62                                      4.30                                         0.00                                            46.08    __________________________________________________________________________

                                      TABLE IX    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    H.sub.2 FeOs.sub.3 (CO).sub.13.2-amino pyridine - Catalyst #6    Activated one hour under vacuum and 1.25 hours under H.sub.2 at    250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.00  200 250 16.82                            16.82  17.01                                      6.19                                         1.41                                            75.39    2     2.00  200 250  7.88                             7.77  31.05                                      10.82                                         2.68                                            55.45    3     19.00 200 250 13.42                            13.42  23.54                                      6.13                                         2.13                                            68.20    4     27.50 200 250 13.22                            13.22  25.14                                      5.32                                         2.97                                            66.57    5     44.50 200 250 14.66                            14.53  26.82                                      5.27                                         4.19                                            63.72    6     48.25 200 275 32.18                            31.18  32.00                                      7.16                                         2.92                                            57.92    7     117.50                200 275 40.15                            33.74  43.71                                      10.64                                         0.69                                            44.96    8     123.00                200 275 42.27                            35.37  43.48                                      10.75                                         0.71                                            45.06    __________________________________________________________________________

                                      TABLE X    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    RuCl.sub.3.2-amino pyridine - Catalyst #8    Activated one hour under vacuum and one hour under H.sub.2 at 250°    C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                          C.sub.2.sup.=                                             C.sub.3.sup.+    __________________________________________________________________________    1     0.72  200 250 20.29                            20.05  18.79                                      2.56                                          0.00                                             78.65    2     1.67  200 250 28.30                            27.82  19.74                                      2.32                                          0.00                                             77.94    3     2.66  200 250 26.54                            26.22  20.16                                      1.99                                          0.00                                             77.85    4     19.70 200 250 15.81                            15.81  23.07                                      0.00.sup.a                                          0.00                                             76.93    5     23.95 200 250 16.48                            16.48  21.63                                      2.54                                          0.00                                             75.83    6     43.95 200 250 16.07                            16.07  20.44                                      1.88                                          0.00                                             77.68    7     45.45 200 275 30.54                            30.41  41.55                                      3.63                                          0.00                                             54.82    8     47.45 200 275 33.40                            33.28  41.29                                      4.52                                          0.00                                             54.19    9     48.45 200 275 33.07                            32.95  42.63                                      4.76                                          0.00                                             52.61    __________________________________________________________________________     .sup.a Trace ethane formed missed by integrator

                                      TABLE XI    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    H.sub.2 FeRu.sub.3 (CO).sub.12.Dipyridyl - Catalyst #12    Activated one hour under vacuum and one hour under H.sub.2 at 250°    C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     2.25  200 250 18.08                            16.67  27.21                                      4.46                                         0.00                                            68.33    2     4.00  200 250 20.93                            19.98  26.95                                      3.96                                         0.00                                            69.09    3     5.00  200 250 23.66                            22.73  19.83                                      4.47                                         0.00                                            75.70    4     21.17 200 250 20.93                            20.59  24.19                                      2.75                                         0.00                                            73.06    5     26.50 200 250 18.54                            18.17  28.19                                      3.40                                         0.00                                            68.41    6     45.50 200 250 18.06                            17.82  28.81                                      3.77                                         0.00                                            67.42    7     51.00 200 250 18.26                            18.01  28.17                                      3.37                                         0.00                                            68.36    8     117.50                200 250 17.82                            17.71  29.25                                      2.94                                         0.00                                            67.81    9     122.50                200 275 49.66                            48.28  35.78                                      5.22                                         0.00                                            59.00    10.sup.          125.00                200 275 51.03                            49.57  35.86                                      4.77                                         0.00                                            59.37    11.sup.          144.00                200 275 51.92                            50.62  33.83                                      4.60                                         0.00                                            61.57    12.sup.a          149.00                200 250 18.58                            18.31  29.63                                      4.74                                         0.00                                            65.63    13.sup.a          165.50                200 250 39.12                            38.89  22.41                                      2.26                                         0.00                                            75.33    14.sup.a          167.50                200 250 38.70                            38.47  22.47                                      2.30                                         0.00                                            75.23    15.sup.b          171.50                200 250 15.48                            15.41  26.37                                      3.12                                         0.00                                            70.49    16.sup.b          189.50                200 250 16.06                            16.00  26.15                                      2.68                                         0.00                                            71.17    __________________________________________________________________________     .sup.a 350 psig (2413 kPa)     .sup.b 80 psig (552 kPa)

                                      TABLE XII    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    H.sub.4 Ru.sub.4 (CO).sub.12.Dipyridyl - Catalyst #13    Activated one hour under vacuum and one hour under H.sub.2 at 250°    C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.50  200 250 22.19                            22.19  52.61                                      5.59                                         0.00                                            41.80    2     3.50  200 250 22.64                            22.64  50.10                                      5.31                                         0.00                                            44.59    3     20.50 200 250 24.05                            25.05  45.41                                      4.18                                         0.00                                            50.41    4     28.00 200 250 23.58                            23.58  45.63                                      4.39                                         0.00                                            49.98    5     45.50 200 250 22.64                            22.64  46.30                                      4.34                                         0.00                                            49.36    6     51.00 200 250 23.04                            23.04  44.81                                      4.41                                         0.00                                            50.78    7     69.50 200 250 23.43                            23.43  43.99                                      3.92                                         0.00                                            52.09    8     73.50 200 275 32.26                            32.26  67.45                                      5.39                                         0.00                                            27.16    __________________________________________________________________________

                                      TABLE XIII    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    MnCo(CO).sub.9.Dipyridyl - Catalyst #14    Activated one hour under vacuum and one hour under H.sub.2 at 250°    C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                          C.sub.2.sup.=                                              C.sub.3.sup.+    __________________________________________________________________________    1     3.00  200 250 8.82                            8.82   10.32                                      0.00.sup.a                                          0.00.sup.a                                              89.68    2     4.50  200 250 9.91                            9.91   10.71                                      0.00.sup.a                                          0.00.sup.a                                              89.29    3     21.50 200 250 8.89                            8.89    7.03                                      0.98                                          9.17.sup.b                                              82.81    4     24.50 200 275 26.57                            25.53  12.01                                      3.97                                          2.54                                              81.48    5     28.50 200 275 27.65                            26.64  11.72                                      4.09                                          1.97                                              82.22    6     46.50 200 275 21.78                            21.02  13.09                                      4.56                                          1.56                                              80.79    7     52.50 200 275 20.12                            19.52  16.18                                      4.84                                          1.33                                              77.65    8     70.50 200 275 16.68                            16.27  17.58                                      4.05                                          0.83                                              77.54    __________________________________________________________________________     .sup.a Trace peaks present could not be distinguished from noise by     integrator     .sup.b Overestimated due to noise

                                      TABLE XIV    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    RuCl.sub.3.Dipyridyl - Catalyst #15    Activated one hour under vacuum and one hour under H.sub.2 at 250°    C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     1.00  200 250 7.24                            7.24   24.67                                      2.95                                         0.00                                            72.38    2     4.00  200 250 5.92                            5.92   31.94                                      0.00                                         0.00                                            68.06    3     20.25 200 250 3.42                            3.42   26.69                                      0.00                                         0.00                                            73.31    4     22.50 200 275 6.45                            6.45   50.24                                      0.00                                         0.00                                            49.76    5     26.50 200 275 6.85                            6.85   47.24                                      6.59                                         0.00                                            46.17    6     28.00 200 275 6.72                            6.72   46.89                                      6.37                                         0.00                                            46.74    7     93.00 200 275 5.59                            5.59   41.96                                      11.07                                         0.00                                            46.97    .sup. 8.sup.a          98.00 200 275 5.30                            5.30   41.19                                      9.22                                         0.00                                            49.59    .sup. 9.sup.a          100.00                200 275 6.67                            6.67   49.04                                      7.68                                         0.00                                            43.28    __________________________________________________________________________     .sup.a Reactor Pressure = 250 psig (1724 kPa)

                                      TABLE XV    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru.sub.3 (CO).sub.12.Dipyridyl - Catalyst #16    Activated one hour under vacuum and 1.5 hours under H.sub.2 at    250° C.    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     3.33  200 250 38.95                            38.95  42.73                                      4.97                                         0.00                                            52.30    2     6.67  200 250 39.36                            39.36  40.09                                      4.64                                         0.00                                            55.27    3     24.50 200 250 38.77                            38.77  39.04                                      4.33                                         0.00                                            56.63    4     28.00 200 275 50.10                            50.02  56.24                                      6.25                                         0.00                                            37.51    5     30.33 200 275 53.38                            53.37  58.75                                      6.66                                         0.00                                            34.57    6     118.91                400 275 56.73                            56.67  61.87                                      6.07                                         0.00                                            32.06    7     120.64                400 275 56.90                            56.86  61.41                                      6.03                                         0.00                                            32.56    8     124.39                400 250 47.78                            47.78  32.78                                      3.49                                         0.00                                            63.73    9     125.74                400 250 50.51                            50.51  31.46                                      3.29                                         0.00                                            65.25    10    142.92                400 250 56.53                            56.53  28.30                                      2.96                                         0.00                                            68.74    11    149.85                400 250 57.05                            57.05  28.00                                      2.88                                         0.00                                            69.12    12    172.93                400 225 43.84                            43.84  12.38                                      0.74                                         0.00                                            86.88    13    191.13                400 225 50.23                            50.23  11.24                                      0.72                                         0.00                                            88.04    14    193.35                400 225 50.29                            50.29  11.27                                      0.69                                         0.00                                            88.04    15    196.35                400 175 13.58                            13.58   1.32                                      0.00                                         0.00                                            98.68    16    214.93                400 175 11.60                            11.60   1.63                                      0.00                                         0.00                                            98.37    __________________________________________________________________________

                                      TABLE XVI    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    RuCl.sub.3.Dipyridyl - Catalyst #17    No activation other than that noted on Table I    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                          C.sub.2.sup.=                                             C.sub.3.sup.+    __________________________________________________________________________    1     2.75  200 250 6.04                            6.04   20.95                                      0.00                                          0.00                                             79.05    2     6.83  200 250 6.11                            6.11   20.45                                      0.00                                          0.00                                             79.55    3     27.16 200 250 5.99                            5.99   18.35                                      0.00                                          0.00                                             81.65    4     29.33 200 275 12.73                            12.73  39.62                                      5.41                                          0.00                                             54.97    5     120.25                200 275 20.11                            20.11  39.23                                      3.96                                          0.00                                             56.80    6     144.21                200 275 21.67                            21.67  37.14                                      3.84                                          0.00                                             59.02    7     168.23                200 275 22.55                            22.55  37.62                                      4.05                                          0.00                                             58.33    HYDROGEN TREATMENT: 250° C., 50 PSIG, 40 SCCM*, ONE HOUR    8     17.75 200 250 19.69                            19.69  18.41                                      2.12                                           0.00                                             79.73    9     20.02 200 250 19.64                            19.64  18.22                                      0.00.sup.a                                          0.00                                             81.78    10    24.27 200 275 28.98                            28.98  42.17                                      4.64                                          0.00                                             53.19    11    41.60 200 275 29.55                            29.46  40.93                                      4.25                                          0.00                                             54.82    __________________________________________________________________________     .sup.a Trace Ethane formed, missed by integrator     *Standard Cubic Centimeters per Minute

                                      TABLE XVII    __________________________________________________________________________    CO Conversion and Light Product Selectivities for    Ru on Al.sub.2 O.sub.3 - Comparative    Reaction Conditions CO Conversion (%)    On-Stream   GHSV                    Temp.   To     Product Selectivity (%)    Sample #          Time (hr)                (hr.sup.-1)                    (°C.)                        Total                            Hydrocarbon                                   C.sub.1                                      C.sub.2                                         C.sub.2.sup.=                                            C.sub.3.sup.+    __________________________________________________________________________    1     0.50  200 250 54.80                            47.07  70.94                                      3.14                                         0.00                                            25.92    2     1.00  200 250 58.61                            50.71  66.41                                      3.40                                         0.00                                            30.19    3     18.50 200 250 95.39                            91.58  7.75                                      1.71                                         0.00                                            90.54    4     21.00 400 250 87.87                            85.73  9.22                                      1.86                                         0.00                                            88.92    5     24.50 400 225 70.65                            69.85  8.75                                      1.55                                         0.15                                            89.55    6     42.00 400 225 57.97                            57.86  8.60                                      0.86                                         0.00                                            90.54    7     45.00 400 225 53.25                            53.23  9.70                                      1.03                                         0.00                                            89.27    8     48.25 400 225 53.28                            53.27  9.63                                      0.92                                         0.00                                            89.45    __________________________________________________________________________

For a comparison with a conventional Fischer-Tropsch catalyst, Ru on Al₂O₃ was prepared by a conventional literature procedure and tested in thereactor system. From Table XVII it can be seen that the conventionalRu/Al₂ O₃ catalyst was more active at 250° C. than any polymer boundcatalyst. However, at 225° C. (53% conversion), the Ru₃ (CO)₁₂ catalyst#16 was nearly as active (≈50% conversion). Thus polymer bound catalystscan achieve acceptable Fischer-Tropsch activity at lower temperatures,thus saving energy. Tables XVIII through XXVI set out productselectivities for selected catalysts at different times during a run andat different GHSV, temperatures and pressures. It is evident from thedata that Catalyst #14 (MnCo(CO)₉ -Dipyridyl) and Catalyst #6 (H₂ FeOs₃(CO)₁₃ -2Amino Phenol) produced a substantial amount of olefins.

                  TABLE XVIII    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    Ru.sub.3 (CO).sub.12.Anthranilic Acid at 250° C., 1034 kPa (150    psig)    200 hr.sup.-1 - Catalyst #3    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            24.20  4.56   6.33   6.09 3.84   0.67 54.31    Olefin %            --     0.00   10.18  24.72                                      12.50  NA   NA    ______________________________________

                  TABLE XIX    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    H.sub.2 FeRu.sub.3 (CO).sub.13.Anthranilic Acid at 250° C.    1034 kPa (150 psig), 200 hr.sup.-1,    After 23 hours on stream - Catalyst #1    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            22.7   3.05   3.08   3.08 2.12   0.59 65.38    Olefin %            --     17.56  36.02  38.48                                      37.39  NA   NA    ______________________________________

                  TABLE XX    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    K.sub.2 Ru.sub.6 (CO).sub.16.Anthranilic Acid at 250° C., 1034 kPa    (150 psig)    200 hr.sup.-1 After 25 hours on stream - Catalyst #2    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            20.84  2.56   1.71   2.04 1.91   0.96 69.98    Olefin %            --     0.00   40.38  43.94                                      47.61  NA   NA    ______________________________________

                  TABLE XXI    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    H.sub.2 FeOs.sub.3 (CO).sub.13.2Aminopyridine    at 1034 kPa (150 psig) - Catalyst #6    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            26.82  9.46   13.54  8.32 3.05   0.42 38.39    Olefin %            --     51.47  63.05  58.85                                      40.30  NA   NA    ______________________________________

                  TABLE XXII    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    H.sub.4 Ru.sub.4 (CO).sub.12.Dipyridyl at 250° C. - Catalyst #13    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            43.99  3.92   4.56   4.08 3.16   2.96 37.33    Olefin %            --     0.00   12.63  24.65                                      13.53  NA   NA    ______________________________________

                  TABLE XXIII    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    MnCo(CO).sub.9.Dipyridyl at 275° C. - Catalyst #14    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            11.72  6.06   7.33   4.87 3.28   1.48 65.26    Olefin %            --     35.12  82.12  78.56                                      77.17  NA   NA    ______________________________________

                  TABLE XXIV    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    RuCl.sub.3.Dipyridyl at 275° C. - Catalyst #15    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            37.62  4.05   4.07   3.47 3.11   [52.68].sup.a    Olefin %            --     25.88  47.75  56.31                                      60.07  NA    ______________________________________     .sup.a C.sub.6-8 and C.sub.9+  peaks combined

                  TABLE XXV    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    Ru.sub.3 (CO).sub.12.Dipyridyl at 250° C. - Catalyst #16    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            28.00  2.88   5.13   4.91 2.83   2.54 53.71    Olefin %            --     0.00   38.02  44.82                                      24.02  NA   NA    ______________________________________

                  TABLE XXVI    ______________________________________    C.sub.1 -C.sub.9 + Product Selectivities and Olefin Fractions for    RuCl.sub.3.Dipyridyl at 225° C. (25 hours on stream) Catalyst #17    Carbon Number    1          2      3        4    5      6-8  9+    ______________________________________    Carbon %            9.63   1.16   9.65   11.08                                      5.45   1.28 61.75    Olefin %            --     20.07  68.37  63.90                                      59.20  NA   NA    ______________________________________

The discovery of the instant invention can be more fully appreciatedwhen one realizes that modification of the polymer bound catalyst can bemade to achieve certain desired results from the vapor phaseFisher-Tropsch reaction. Tables XXVII and XXVIII demonstrate that themetal affects selectivity.

                  TABLE XXVII    ______________________________________    Methane Selectivity Comparison for    Three Ru.Dipyridyl Catalysts at 250° C.                        On-Stream Methane    #     Catalyst      Time (hr) Selectivity (%)    ______________________________________    17    RuCl.sub.3 -- 27.16     18.35    16    Ru.sub.3 (CO).sub.12 --                        24.50     39.04    13    H.sub.4 Ru.sub.4 (CO).sub.12 --                        28.00     45.63    ______________________________________

                  TABLE XXVIII    ______________________________________    C.sub.2 -C.sub.5 Olefin Fraction Comparison for    Five Dipyridyl Catalysts               On               Stream        Olefin Percent (%)               Time  Temp    Carbon Number    #   Catalyst     (hr)    (°C.)                                   2    3    4    5    ______________________________________    16  Ru.sub.3 (CO).sub.12                     148.00  250   0.00 38.02                                             44.82                                                  24.02    17  RuCl.sub.3   169.45  275   25.88                                        47.75                                             56.31                                                  60.07    13  H.sub.4 Ru.sub.4 (CO).sub.12                     72.38   250   0.00 12.63                                             24.65                                                  13.53    12  H.sub.2 FeRu.sub.3 (CO).sub.13                     28.32   250   0.00 16.76                                             26.85                                                  14.39    14  MnCo(CO).sub.9                     24.80   275   35.12                                        82.18                                             78.56                                                  77.17    ______________________________________

Table XXIX sets out data on MnCo catalysts polymer supported vs.conventionally supported. The conventional catalyst data is from theliterature.

                                      TABLE XXIX    __________________________________________________________________________    Comparison of Polymer Bound and Conventional MnCo Catalysts for    Light Olefins Production from Synthesis Gas                                          Results    Catalyst             Reaction               C.sub.2 -C.sub.4              Total  Mn/Co                         Temp.                             Press                                 Space Velocity                                          CO Conv.                                                Olefin    # Components              Metal Wt %                     Ratio                         (°C.)                             (psig)                                 (cm.sup.3 /sec/gm cat.)                                          (%)   Percent    __________________________________________________________________________    14      MnCo(CO).sub.9 --               6.sup.a                     .sup. 1/1.sup.a                         275 150 7.4      20    65.57      Dipyridyl      MnCo--Al.sub.2 O.sub.3              27     1/2 242 100 0.42     36.0  0      MnCo--Al.sub.2 O.sub.3              27     1/2 279 100 0.42     3.0   80.77      with K.sub.2 O    __________________________________________________________________________     .sup.a Estimated

DEACTIVATION OF CATALYST

The novel catalysts of the invention have demonstrated Fischer-Tropschactivity for extended periods of time (in excess of 200 hours) withoutsignificant deactivation. Most significantly, one polymer bound catalyst(Catalyst #6, Table IX) demonstrated increasing activity with time onstream.

Catalyst #16 was submitted for elemental analysis prior and subsequentto the run set out in Table XV. It was determined that ruthenium was notlost during the Fischer-Tropsch reaction. This is very important sincethe catalyst still contained all of the valuable ruthenium metal. Themetal may be recovered by burning the resin.

In the past, only conventional catalysts were used for the vapor phaseFischer-Tropsch reaction. Conventional catalysts generally are supportedon either silica or alumina if they are supported at all. They aresynthesized by precipitation or fusion techniques and contain no ligandbridges thus making it difficult to obtain small metal clusters whichare desired for the Fischer-Tropsch reaction.

It is clear from these results that the catalytic system of theinvention is sensitive and that the exact constitution thereof iscritical in obtaining the desired results. The instant inventionprovides a significant advance in the Fischer-Tropsch reaction since thereaction conditions are mild and the resultant products are notcontaminated with catalyst. This invention being thus described, it willbe obvious that the same may be varied in many ways. Such variations arenot to be regarded as a departure from the scope of the invention, andall such modifications are intended to be included within the scope ofthe following claims.

What we claim is:
 1. In a process for the conversion of synthesis gas tohydrocarbons which comprises contacting said synthesis gas with acatalyst in the vapor phase at a temperature from 175° C. to 300° C. anda pressure of at least 1000 kPa, the improvement comprising using assaid catalyst a catalyst represented by the structural formula: ##STR3##wherein ○P represents a crosslinked macroreticular polystyrene resinwhich has a crosslink density of at least 5%;x is 0 or 1; L represents aligand selected from the group consisting of bipyridyl, 2-aminopyridine,2-amino phenol, 2-imino pyridine, sodium anthranilate and potassiumanthranilate; y is an integer from 1 through 8; when y equals 1, Mrepresents a Group VIII metal from the Periodic Table and when y is from2 through 8, M represents one or more metals selected from the groupconsisting of Group VIII metals of the the Periodic Table, manganese,potassium and sodium; with the proviso that at least one M is a GroupVIII metal; R represents the same or different radical selected from thegroup consisting of hydrogen, carbonyl and halogen; and n represents aninteger from 3 through
 24. 2. A process according to claim 1 wherein Lis dipyridyl and (M)_(y) (R)_(n) is Ru₃ (CO)₁₂.
 3. A process accordingto claim 1 characterized in that L is 2-amino phenol and (M)_(y) (R)_(n)is H₂ FeOs₃ (CO)₁₃.
 4. A process according to claim 1 characterized inthat the temperature is from 225° C. to 250° C.